WO2019164341A1 - Spiro compound and organic light-emitting device comprising same - Google Patents

Abstract

The present specification relates to a spiro compound of chemical formula 1 and an organic light-emitting device comprising same.

Description

Spiro compound and organic light emitting device comprising the same

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2018-0021868 filed with the Korea Patent Office on February 23, 2018, the entire contents of which are incorporated herein.

The present specification relates to a spiro compound and an organic light emitting device formed using the spiro compound.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuing need for the development of new materials for such organic light emitting devices.

The present specification provides a spiro compound and an organic light emitting device including the same.

According to an exemplary embodiment of the present specification to provide a spiro compound represented by the formula (1).

[Formula 1]

[Formula 2]

[Formula 3]

R1 is a substituent represented by Formula 2 or 3,

In Chemical Formulas 1 to 3,

R2 to R6 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted Aryl group or a substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring,

L is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

a, b and f are each an integer of 0 to 7,

c is an integer from 0 to 3,

when c is 0, L is a substituted or unsubstituted heteroarylene group,

d is an integer of 0 to 8,

e is an integer from 0 to 3,

When a is plural, R2 is the same as or different from each other,

When b is plural, R3 is the same as or different from each other,

When d is plural, R4 is the same as or different from each other,

When e is plural, R5 is the same as or different from each other,

When f is plural, R6 is the same as or different from each other.

In addition, the present specification is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the spiro compound.

The spiro compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device having thermal stability, and by using the same, the efficiency of the organic light emitting device may be improved, and the driving voltage and / or lifespan characteristics may be improved. Do.

In particular, the triplet energy is increased by fixing the substituent at the 4,4 'position, and P-type and N-type substituents are introduced at the substitution positions, respectively, to be applied as a bipolar host.

1 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.

2 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.

[Description of the code]

1: substrate

2: first electrode

3: organic material layer

4: second electrode

5: light emitting layer

Hereinafter, this specification was demonstrated in more detail.

The present specification provides a spiro compound represented by Chemical Formula 1.

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components, unless specifically stated otherwise.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.

As used herein, the term "substituted or unsubstituted" is deuterium; Nitrile group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group, or one or two or more substituents selected from the group consisting of, or two or more substituents among the substituents exemplified above, or a substituent. For example, "a substituent to which two or more substituents are linked" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.

In the present specification, the halogen group may be a fluoro group, a chloro group, a bromo group, an iodo group, or the like.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. It is not.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, penalenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. no.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

,

,

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

And

And so on. However, the present invention is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolinyl group (phenanthroline), isooxazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzofuranyl group and the like, but is not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may simultaneously include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.

In the present specification, the arylene group is the same as the definition of an aryl group except that it is divalent.

In the present specification, the heteroarylene group is the same as the definition of the heteroaryl group, except that it is divalent.

According to an exemplary embodiment of the present specification, Chemical Formula 2 is represented by any one of the following Chemical Formulas 4 to 6.

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6, R4 is as defined in Chemical Formula 1,

R7 to R9 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted Aryl group or substituted or unsubstituted heteroaryl group,

Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted Aryl group or substituted or unsubstituted heteroaryl group,

d is an integer of 0 to 7,

g is an integer from 0 to 8,

h is an integer from 0 to 7,

i is an integer from 0 to 10,

when g is plural, R7 is the same as or different from each other,

when h is plural, R8 is the same as or different from each other,

When i is plural, they are the same as or different from each other.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 7 to 9.

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 7 to 9, R2 to R6 and a to f are as defined in Formulas 1 to 3,

R9 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, or substituted or unsubstituted hetero An aryl group,

Ar3 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, or substituted or unsubstituted hetero An aryl group,

i is an integer from 0 to 10, and when i is plural, R9 are the same as or different from each other.

According to an exemplary embodiment of the present specification, L is a direct bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, L is a direct bond, an arylene group having 6 to 20 carbon atoms, or a heteroarylene group containing N, O, or S having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, L is a direct bond, a monocyclic arylene group having 6 to 20 carbon atoms, a polycyclic arylene group having 10 to 20 carbon atoms, or N, O, or S containing 3 to 20 carbon atoms Heteroarylene group.

According to an exemplary embodiment of the present specification, L is a direct bond, a monocyclic arylene group having 6 to 20 carbon atoms, a polycyclic arylene group having 10 to 20 carbon atoms, or N, O, or S containing 3 to 20 carbon atoms Heteroarylene group.

According to an exemplary embodiment of the present specification, L is a direct bond, a bivalent phenyl group, a bivalent biphenyl group, a bivalent terphenyl group, a bivalent naphthyl group, a bivalent fluorene group, a bivalent carbazole group, a divalent triazine group, A divalent pyrimidine group, a bivalent pyridine group, a bivalent dibenzothiophene group, or a bivalent dibenzofuran group.

According to an exemplary embodiment of the present specification, L is a direct bond, a divalent phenyl group, or a divalent dibenzofuran group.

According to an exemplary embodiment of the present specification, when c is 0, L is a substituted dibenzofuran group.

According to an exemplary embodiment of the present specification, when c is 0, L is an unsubstituted dibenzofuran group.

According to an exemplary embodiment of the present specification, R2 to R10 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or An unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present specification, the R2 to R10 are the same as or different from each other, and each independently hydrogen; Nitrile group; Halogen group; An alkyl group having 1 to 10 carbon atoms; A silyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Or a substituted or unsubstituted N, O, or S-containing heteroaryl group having 3 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, the R2 to R10 are the same as or different from each other, and each independently hydrogen; Nitrile group; Halogen group; An alkyl group having 1 to 10 carbon atoms; A silyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; Aryl groups having 6 to 20 carbon atoms; Or an N, O, or S-containing heteroaryl group having 3 to 10 carbon atoms unsubstituted or substituted with an aryl group having 6 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, the R2 to R10 are the same as or different from each other, and each independently hydrogen; Nitrile group; F; Cl; Br; I; Methyl group; Ethyl group; Profile group; Isopropyl group; Butyl group; Terbutyl group; Pentyl group; Hexyl group; Heptyl group; Octyl group; Nonyl group; Decyl group; A silyl group unsubstituted or substituted with a methyl group; Methoxy group; Ethoxy group; Propoxy group; Butoxy group; Terbutoxy group; Pentoxy group; Phenyl group; Biphenyl group; Terphenyl group; Naphthyl group; Anthracene groups; Phenanthrene group; Pyridine groups unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; Pyrimidine groups unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; Triazine groups unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; Carbazole groups unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; Dibenzofuran group unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group; Or a dibenzothiophene group unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group.

According to an exemplary embodiment of the present specification, the R2 to R10 are the same as or different from each other, and each independently hydrogen; Or a carbazole group unsubstituted or substituted with a phenyl group, a naphthyl group, or a biphenyl group.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently contain a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted N, O, or S It is a C3-C20 heteroaryl group.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a monocyclic aryl group having 6 to 20 carbon atoms, or a polycyclic aryl group having 10 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, and a fluorene group. Pyrene group or triphenylene group.

According to an exemplary embodiment of the present specification, Ar1 to Ar3 are the same as or different from each other, and each independently a phenyl group, a biphenyl group, or a naphthyl group.

According to another exemplary embodiment of the present specification, the spiro compound of Formula 1 may be represented by any one of the following structural formulas.

In addition, the present specification is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the spiro compound.

The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that at least one organic material layer is formed using the above-described compound.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers. In addition, the organic material layer may include one or more layers of an electron transport layer, an electron injection layer, and a layer for simultaneously transporting and transporting electrons, and one or more of the layers may include the compound.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIG. 1, but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which a first electrode 2, an organic material layer 3, and a second electrode 4 are sequentially stacked on a substrate 1.

2 illustrates a structure of an organic light emitting device in which a first electrode 2, a light emitting layer 5, and a second electrode 4 are sequentially stacked on a substrate 1. In FIG. 2, an organic material layer may be added between the first electrode, the light emitting layer, and the light emitting layer and the second electrode. Examples of the organic material layer that may be added include, but are not limited to, a hole injection layer, a hole transport layer, a hole injection and transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer.

1 and 2 illustrate an organic light emitting diode and are not limited thereto.

In an exemplary embodiment of the present invention, the organic material layer including the spiro compound of Formula 1 includes a light emitting layer, and the light emitting layer includes the spiro compound of Formula 1.

In an exemplary embodiment of the present invention, the organic material layer including the spiro compound of Chemical Formula 1 includes a light emitting layer, and includes the spiro compound of Chemical Formula 1 as a host of the light emitting layer.

In an exemplary embodiment of the present invention, the dopant of the light emitting layer includes one or more compounds having a gap ΔE _st ≦ 0.2 eV between the lowest triplet state T1 and the first excited singlet state S1.

In measuring the ΔE _st , the UV-vis absorption spectrum was measured using V-730 manufactured by JASCO Corporation, and the photoluminescence spectrum in the film deposition state and the photoluminescence spectrum in the low-temperature state were Perkin Elmer. It was measured using LS-55 of the company, and the content of the compound 1 was measured in liquid N 1 -10 ^-5 M using HPLC grade THF as a solvent.

In an exemplary embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes a host and a dopant in a weight ratio of 1:99 to 50:50.

In an exemplary embodiment of the present invention, the organic material layer includes a light emitting layer, and includes an organic compound or a metal complex compound as a dopant in the light emitting layer.

In one embodiment of the present invention, the light emitting layer includes a phosphorescent dopant.

In one embodiment of the present invention, the light emitting layer includes a phosphorescent host.

In an exemplary embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes the spiro compound of Formula 1 as a phosphorescent host of the light emitting layer.

In one embodiment of the present invention, the light emitting layer includes an iridium complex as a dopant.

In an exemplary embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes any one of the following compounds as a dopant.

For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. To form an anode, an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an organic material layer including the spiro compound of Formula 1 thereon, and then a material that can be used as a cathode thereon. It can be prepared by vapor deposition. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO ₂ : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organics, quinacridone-based organics, and perylene-based Organic compounds, anthraquinones and polyaniline and poly-compounds of conductive polymers, and the like, but are not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic compounds include spiro compounds, dibenzofuran derivatives, and ladder furan compounds. Compounds, pyrimidine derivatives, and the like, but is not limited thereto.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer is formed using the spiro compound.

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, the anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on the substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. And an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The present specification also provides a method of manufacturing an organic light emitting device formed using the spiro compound.

Specifically, in one embodiment of the present specification, preparing a substrate; Forming a cathode or anode on the substrate; Forming at least one organic layer on the cathode or anode; And forming an anode or a cathode on the organic material layer, wherein at least one layer of the organic material layer is formed using the spiro compound.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a material used.

The organic light emitting device according to the present disclosure may synthesize all the compounds described in the specification by changing the type of substituents in the following Preparation Examples.

<General Production Example >

Synthesis of C

In a nitrogen atmosphere, 20 mmol of Sm A, 22 mmol of Sm B and 2 mol% of tetrakis triphenylphosphinepalladium were added to 60 ml of tetrahydrofuran, and 60 mmol of potassium carbonate was dissolved in 30 ml of water. After stirring for 12 hours at 80 ° C. the reaction was terminated and cooled to room temperature to separate the water and the organic layer. Only the organic layer was received and stirred with anhydrous magnesium sulfate. Silica pad (silica pad) was filtered, column purified by solution concentration under reduced pressure, and intermediate C was obtained in 75% yield.

Synthesis of F

Under nitrogen atmosphere, intermediate C 20mmol and Sm D 20mmol were completely dissolved in 60ml of toluene, and then, 24 mmol of sodium-tert-butoxide was added thereto, and the mixture was stirred while increasing the temperature until reflux. When refluxed, 1 mol% of bis (tri-tert-butylphosphine) palladium was slowly added dropwise. After 6 hours, the reaction was completed, the temperature was lowered to room temperature, concentrated under reduced pressure, and column purified to obtain Compound F in 65% yield.

Synthesis of G

In a nitrogen atmosphere, 20 mmol of intermediate C, 22 mmol of Sm E and 1 mol% of bis (tri-tert-butyl phosphine) palladium (BIs) were added to 60 ml of tetrahydrofuran and 60 mmol of potassium carbonate was added to 30 ml of water. Melt and mix. After stirring for 12 hours at 80 ° C. the reaction was terminated and cooled to room temperature to separate the water and the organic layer. Only the organic layer was received and stirred with anhydrous magnesium sulfate. Silica pad (silica pad) was filtered and column purified by solution concentration under reduced pressure to give compound G in 73% yield.

Of compound 1 Production Example

In a nitrogen atmosphere, the compound 4-bromo-4'-chloro-9,9'-spirobifluorene (10.0 g, 23.36 mmol) and 9H-carbazole (3.9 g, 23.36 mmol) were completely dissolved in 70 ml of xylene. Then, potassium hydroxide (2.6 g, 46.72 mmol) and 1,10-phenanthroline (6.7 g, 37.38 mmol) were added thereto, and the mixture was stirred while raising the temperature to reflux. Once refluxed, copper iodide (0.45 g, 2.34 mmol) was added to the solid several times. After 8 hours, the reaction was completed, the temperature was lowered to room temperature, silica filtration, concentration under reduced pressure, and column purification to prepare Intermediate 1-1 (8.18 g, 68% yield).

MS [M + H] ⁺ = 516

Intermediate 1-1 (8.18g, 15.88mmol), (3-cyanophenyl) boronic acid (2.57g, 17.47mmol) and bis (tri-t-butylphosphine) palladium (BIs (tri-tert) under nitrogen atmosphere -butylphosphine) palladium) (0.08g, 0.16mmol) was added to 45ml of tetrahydrofuran and potassium carbonate (6.6g, 47.64mmol) was dissolved in 20ml of water. After stirring for 12 hours at 80 ° C. the reaction was terminated and cooled to room temperature to separate the water and the organic layer. Only the organic layer was received and stirred with anhydrous magnesium sulfate. Silica pad filtration and solution purification under reduced pressure were followed by column purification to afford compound 1 (6.56 g, 71% yield).

MS: [M + H] &lt; + &gt; = 583.

Of compound 2 Production Example

The compound was reacted and purified in the same manner as in the synthesis of Compound 1, except that Intermediate 1-1 (10.0 g, 21.35 mmol) and dibenzo [b, d] furan-4-ylboronic acid (4.5 g, 21.35 mmol) were used. 2 (9.17 g, 73% yield) was obtained.

MS: [M + H] &lt; + &gt; 648

Of compound 3 Production Example

Intermediate 1-1 (10.0 g, 21.35 mmol) and 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) dibenzo [b, d] furan Reaction and purification were carried out in the same manner as in the synthesis of Compound 1, except for using 2-carbonitrile (6.8 g, 21.35 mmol) to obtain Compound 3 (10.44 g, 80% yield).

MS: [M + H] &lt; + &gt; = 673

Of compound 4 Production Example

Intermediate 1- except that 4-bromo-4'-chloro-9,9'-spirobifluorene (10.0 g, 23.36 mmol) and 2-phenyl-9H-carbazole (5.68 g, 23.36 mmol) were used. Reaction and purification were conducted in the same manner as in the synthesis of 1, to obtain Intermediate 4-1 (9.1 g, 66% yield).

MS: [M + H] &lt; + &gt; 592

Compound 4 was reacted and purified in the same manner as in the synthesis of Compound 1, except that Intermediate 4-1 (9.1 g, 15.39 mmol) and (3,5-dithiophenyl) boronic acid (2.9 g, 16.93 mmol) were used. (7.15 g, 68% yield) was obtained.

MS: [M + H] &lt; + &gt; 684

Of compound 5 Production Example

4-bromo-4'-chloro-9,9'-spirobifluorene (10.0 g, 23.36 mmol) and 5-phenyl-5,12-dihydroindolo [3,2-a] carbazole (7.8 g, 23.36 mmol) was reacted and purified in the same manner as in the synthesis of Intermediate 1-1, to obtain Intermediate 5-1 (9.7 g, 61% yield).

MS: [M + H] &lt; + &gt; = 681

The compound was reacted and purified in the same manner as the synthesis of Compound 1, except that Intermediate 5-1 (9.7 g, 14.25 mmol) and dibenzo [b, d] furan-2-ylboronic acid (3.3 g, 15.67 mmol) were used. 5 (8.2 g, 71% yield) was obtained.

MS: [M + H] &lt; + &gt; 813

Of compound 6 Production Example

In a nitrogen atmosphere, 4-bromo-4'-chloro-9,9'-spirobifluorene (10.0 g, 23.36 mmol) and zinc cyanide (1.65 g, 14.02 mmol) were added to 60 ml of dimethylformamide, and the temperature was increased. Stirred. After reflux, tetrakis triphenylphosphine palladium (2.7 g, 2.33 mmol) was added in a batch, and after 3 hours, the reaction was completed, the temperature was lowered to room temperature, silica filtration, concentration under reduced pressure, and column purification. Intermediate 6-1 (6.13 g, 70% yield) was prepared.

MS [M + H] ⁺ = 376

In a nitrogen atmosphere, intermediate 6-1 (6.13 g, 16.34 mmol), 9H-carbazole (2.7 g, 16.34 mmol), and sodium t-butoxide (1.9 g, 19.61 mmol) were added to 45 ml of xylene, and then the temperature was increased and stirred. It was. When refluxed, bis (tri-tert-butylphosphine) palladium (BIs (tri-tert-butylphosphine) palladium) (0.08 g, 0.16 mmol) was dissolved in xylene and slowly added dropwise. After 5 hours, the reaction was completed, the temperature was lowered to room temperature, silica filtration, concentration under reduced pressure, and column purification were performed to obtain compound 6 (5.0 g, 61% yield).

MS [M + H] ⁺ = 507

Of compound 7 Production Example

Synthesis of Compound 6 above with the use of Intermediate 6-1 (6.13 g, 16.34 mmol) and 5-phenyl-5,8-dihydroindolo [2,3-c] carbazole (5.4 g, 16.34 mmol) Reaction and purification were carried out in the same manner to afford compound 7 (6.9 g, 63% yield).

MS: [M + H] &lt; + &gt; 672

Of compound 8 Production Example

4-bromo-4'-chloro-9,9'-spirobifluorene (10 g, 23.36 mmol), indolo [3,2,1-jk] carbazol-10-yl boronic acid (7.3) under nitrogen atmosphere g, 25.69 mmol) and tetrakis triphenylphosphine palladium (0.5 g, 0.47 mmol) were added to 75 ml of tetrahydrofuran and potassium carbonate (9.7 g, 70.08 mmol) was dissolved in 30 ml of water. . After stirring for 12 hours at 80 ° C. the reaction was terminated and cooled to room temperature to separate the water and the organic layer. Only the organic layer was received and stirred with anhydrous magnesium sulfate. After filtration of silica pad (silica pad), the solution was concentrated under reduced pressure and column purified to obtain Intermediate 8-1 (10.0 g, 73%).

MS: [M + H] &lt; + &gt; 590

Except for using Intermediate 8-1 (10.0g, 17.05mmol) and (2-cyanophenyl) boronic acid (2.8g, 18.76mmol), Compound 8 (7.2g) was reacted and purified in the same manner as in the synthesis of Compound 1. , 64% yield).

MS: [M + H] &lt; + &gt; 657

< Example >

A glass substrate coated with a thickness of 1,000 kPa of ITO (indium tin oxide) was put in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

M-MTDATA (60nm) / TCTA (80nm) / Host + 10% Ir (ppy) ₃ on the prepared ITO transparent electrode A light emitting device was constructed in the order of (300 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm), and an organic EL device was manufactured using Compound 1 as the host.

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ and BCP are as follows.

< Experimental Example  1-2>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 2 was used instead of compound 1 in Experimental Example 1-1.

< Experimental Example  1-3>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 3 was used instead of compound 1 in Experimental Example 1-1.

< Experimental Example  1-4>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 4 was used instead of compound 1 in Experimental Example 1-1.

< Experimental Example  1-5>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 5 was used instead of compound 1 in Experimental Example 1-1.

< Experimental Example  1-6>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 6 was used instead of compound 1 in Experimental Example 1-1.

< Experimental Example  1-7>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 7 was used instead of compound 1 in Experimental Example 1-1.

< Experimental Example  1-8>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 8 was used instead of compound 1 in Experimental Example 1-1.

< Comparative example  1-1>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that Comparative Compound 1 was used instead of Compound 1 in Experimental Example 1-1.

< Comparative example  1-2>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that Comparative Compound 2 was used instead of Compound 1 in Experimental Example 1-1.

< Comparative example  1-3>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that Comparative Compound 3 was used instead of Compound 1 in Experimental Example 1-1.

When the electric current was applied to the organic light emitting element produced by Experimental Example 1-1 to 1-8, Comparative Example 1-1, and 1-3, the result of Table 1 was obtained.

Compound (Host) Voltage (V @ 10mA / cm ² ) Efficiency (cd / A @ 10mA / cm ² ) EL peak (nm) Experimental Example 1-1 Compound 1 3.63 44.93 517 Experimental Example 1-2 Compound 2 3.86 42.64 516 Experimental Example 1-3 Compound 3 3.85 43.62 518 Experimental Example 1-4 Compound 4 3.75 42.75 517 Experimental Example 1-5 Compound 5 3.88 42.51 515 Experimental Example 1-6 Compound 6 3.79 42.53 516 Experimental Example 1-7 Compound 7 3.77 44.52 516 Experimental Example 1-8 Compound 8 3.68 42.54 517 Comparative Example 1-1 Comparative Compound 1 5.78 38.47 517 Comparative Example 1-2 Comparative Compound 2 5.90 37.21 517 Comparative Example 1-3 Comparative Compound 3 5.67 36.11 517

As a result, the green organic light-emitting device of Experimental Examples 1-1 to 1-8 using the compound represented by Compounds 1 to 8 according to the present invention as a host material of the light emitting layer, Comparative Example 1- using Comparative Compounds 1 to 3 The green organic light emitting device of 1 to 1-3 showed better performance in terms of current efficiency and driving voltage.

< Experimental Example  2-1>

An organic light emitting diode was manufactured by using Compound 1 as a host of the light emitting material layer. First, a glass substrate with an ITO (including reflector) electrode having a thickness of 40 mm × 40 mm × 0.5 mm was subjected to ultrasonic cleaning for 5 minutes with isopropyl alcohol, acetone, and DI water, and then dried at 100 ° C. Oven. After cleaning the substrate, O ₂ plasma treatment in vacuum for 2 minutes and transferred to the deposition chamber to deposit other layers on top. The organic layer was deposited in the following order by evaporation from a heating boat under about 10 ⁻⁷ Torr vacuum. At this time, the deposition rate of the organic material was set to 1 dl / s.

Hole injection layer (HIL; HAT-CN, 70 kPa), hole transport layer (HTL; NPB, 780 kPa), electron blocking layer (EBL; mCBP, 150 kPa), light emitting material layer (EML; compound 1) 30 wt% doped BDpyInCz with delayed fluorescent material, 350 cc), hole blocking layer (HBL; B3PYMPM; 100 ms), electron transport layer (ETL: TPBi, 250 ms), electron injection layer (EIL; LiF, 8 ms), Cathode (Al; 1000 Å) and CPL (capping layer) were deposited and encapsulated in glass. These layers were transferred into a dry box in the deposition chamber after film deposition and subsequently encapsulated using a UV cured epoxy and a moisture getter.

< Experimental Example  2-2>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that compound 2 was used instead of compound 1 in Experimental Example 2-1.

< Experimental Example  2-3>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that compound 3 was used instead of compound 1 in Experimental Example 2-1.

< Experimental Example  2-4>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that compound 4 was used instead of compound 1 in Experimental Example 2-1.

< Experimental Example  2-5>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that compound 5 was used instead of compound 1 in Experimental Example 2-1.

< Experimental Example  2-6>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that compound 6 was used instead of compound 1 in Experimental Example 2-1.

< Experimental Example  2-7>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that compound 7 was used instead of compound 1 in Experimental Example 2-1.

< Experimental Example  2-8>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that compound 8 was used instead of compound 1 in Experimental Example 2-1.

< Comparative example  2-1>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that Comparative Compound 1 was used instead of Compound 1 in Experimental Example 2-1.

< Comparative example  2-2>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that Comparative Compound 2 was used instead of Compound 1 in Experimental Example 2-1.

< Comparative example  2-3>

The organic light emitting device was manufactured by the same method as Experimental Example 2-1, except that Comparative Compound 3 was used instead of Compound 1 in Experimental Example 2-1.

When the current was applied to the organic light emitting diodes manufactured by Experimental Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-3, the results of Table 2 were obtained.

Compound (Host) Voltage (V @ 500cd / m ² ) EQE (%) CIE x CIE y Experimental Example 2-1 Compound 1 4.35 8.7 0.173 0.266 Experimental Example 2-2 Compound 2 4.68 8.3 0.167 0.240 Experimental Example 2-3 Compound 3 4.29 8.8 0.162 0.204 Experimental Example 2-4 Compound 4 4.63 9.0 0.164 0.255 Experimental Example 2-5 Compound 5 4.40 8.1 0.175 0.259 Experimental Example 2-6 Compound 6 4.37 8.4 0.168 0.261 Experimental Example 2-7 Compound 7 4.40 8.6 0.173 0.270 Experimental Example 2-8 Compound 8 4.58 8.3 0.161 0.258 Comparative Example 2-1 Comparative Compound 1 6.53 6.8 0.211 0.359 Comparative Example 2-2 Comparative Compound 2 6.13 6.5 0.198 0.348 Comparative Example 2-3 Comparative Compound 3 7.03 5.9 0.201 0.337

When the organic compound synthesized according to the present invention is used as a host of the delayed fluorescent layer, the driving voltage is lower and external quantum is lower than that of Comparative Compounds 1 to 3 of Comparative Examples 2-1 to 2-3 as a host. The efficiency (EQE) is improved. As a result, it was confirmed that the organic compound of the present invention was applied to the organic light emitting layer to lower the driving voltage of the light emitting diode, improve the light emission efficiency, and improve the color purity. Therefore, by using the organic light emitting diode to which the organic compound of the present invention is applied, the organic light emitting diode may be utilized in a light emitting device such as an organic light emitting diode display device and / or a lighting device which lowers power consumption and improves luminous efficiency and device life.

Claims (9)

Spiro compounds represented by the following formula (1): [Formula 1]

[Formula 2]

[Formula 3]

R1 is a substituent represented by Formula 2 or 3, In Chemical Formulas 1 to 3, R2 to R6 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted Aryl group or a substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring, L is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group, a, b and f are each an integer of 0 to 7, c is an integer from 0 to 3, when c is 0, L is a substituted or unsubstituted heteroarylene group, d is an integer of 0 to 8, e is an integer from 0 to 3, When a is plural, R2 is the same as or different from each other, When b is plural, R3 is the same as or different from each other, When d is plural, R4 is the same as or different from each other, When e is plural, R5 is the same as or different from each other, When f is plural, R6 is the same as or different from each other. The spiro compound of claim 1, wherein Formula 2 is represented by one of Formulas 4 to 6: [Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6, R4 is as defined in Chemical Formula 1, R7 to R9 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted Aryl group or substituted or unsubstituted heteroaryl group, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted Aryl group or substituted or unsubstituted heteroaryl group, d is an integer of 0 to 7, g is an integer from 0 to 8, h is an integer from 0 to 7, i is an integer from 0 to 10, when g is plural, R7 is the same as or different from each other, when h is plural, R8 is the same as or different from each other, When i is plural, they are the same as or different from each other. The spiro compound of claim 1, wherein Formula 1 is represented by any one of Formulas 7 to 9. [Formula 7]

[Formula 8]

[Formula 9]

In Formulas 7 to 9, R2 to R6 and a to f are as defined in Formulas 1 to 3, R9 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, or substituted or unsubstituted hetero An aryl group, Ar3 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, or substituted or unsubstituted hetero An aryl group, i is an integer from 0 to 10, and when i is plural, R9 are the same as or different from each other. The spiro compound of claim 1, wherein Formula 1 is any one selected from the following compounds:

A first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including one or two or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the spiro compound of any one of claims 1 to 4. Organic light emitting device. The organic light emitting diode of claim 5, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the spiro compound. The organic light emitting device of claim 5, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the spiro compound as a host of the light emitting layer. The dopant of claim 5, wherein the organic material layer includes a light emitting layer, and the compound including at least one compound having a gap ΔE _st ≦ 0.2 eV between the lowest triplet state T1 and the first excited singlet state S1 is ≦ 0.2 eV. The organic light emitting device. The organic light emitting device of claim 5, wherein the organic material layer includes a light emitting layer, and the light emitting layer uses the spiro compound as a phosphorescent host of the light emitting layer.

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